Halogen-naphthalene-ketones and process of preparing them



Patented May 23, 1933 LQIQA'ZU PATENT OFFICE GEORG KRANZLEIN, HEINRICH VOLLMANN, AND ERNEST DIEFE NBAGH, 0F FRANK- FORT-ON-THE-MAIN-HOCHST,

GERMANY, ASSIGNORS TO GENERAL ANILINE \VORKS, INCL, OF NEW YORK, N. Y., A CORPORATION OF DELAWARE HALOGEN-NAPHTHALENE-KETONES AND PROCESS OF PREPARING THEM.

No Drawing. Application filed November 12, 1928, Serial 10.319303, and in Germany November 26, 1927.

The present invention relates to halogenated-naphthalene-ketones and to, a process of preparing them.

By the action of carhoxylic acid chlorides upon naphthalene in the presence of aluminium chloride, mono-ketones are formed. According to the kind of the carboxylic acid and the conditions under which the process is carried out, especially the degree of temperature, there are chiefly produced aor ,8-inono-ketones. The action of carboxylic acid chlorides in the presence of aluminium chlorides upon substitution products of naphthalene has only been fully studied as regards the naphthols and naphthol ethers.

Thus by the action of acetyl chloride and aluminium chloride upon ,B-naphthol, 2- hydroxy-l-acetylnaphthalene is formed (see Fries Berichte der deutschen Chemischen Gesellschaft volume 54, page 711) and by the action of aluminium chloride and hen zoyl chloride upon oc-IlfiPlltl'lOl-BtllYlGtllQI especially l-ethoxy-l-benzoylnaphthalene is obtained (see Scholl Annalen der Chemie volume 398, page 85/86). In these cases the hydroxyland alkoxyl group respectively greatly promotes the reaction of Friedel- Crafts according to known principles' The .action of acetyl chloride upon 41- and B- mono-bromnaphthalene is described by Schweizer in"Berichte der deutschen Chemischen Gesellschaft volume 24, page 55. Nothing has hitherto been published as regards the possibility of applying Friedel- Craft-s reaction to a polyhalogenated-naphthalene.

Now we have found that by causing a compound of the formula ILCQX wherein. ;X stands for halogen or the group -naphthalene characteristic and well defined ketone derivatives may be obtained with. a good yield. Thusfor instance 1.4- as well as 1.5-dichlornaphthalene yield with .benzoyl chloride uniform nionoketone derivatives in approximately quantitative, yield. Substi tuted aroyl chlorides, for instance ortho and para-chlorbenzoyl chloride, alpha naphthoyl chloride, furthermore methoXy-benwherein R stands for alkyl or aryl and one of the Xs for chlorine, the other X for hydrogen.

The halogenated-naphthalene ketones obtainable according to the present invention,

are important intermediate products for the driven out, the mass is'boiled up with soda solution, filtered and the residue is twice boiled with diluted hydrochloric acid and finally washed until neutral. The resulting crude product may be recrystallized from alcohol while addinganimal charcoal- Thus colorless prisms are obtained melting at 104 C. to 105 0.; which, when dissolved in concentrated sulfuric acid give a yellow solution The product probably constitutes the 1.4-dichlor-8-benzoylnaphthalene of the following formula:

CaHa (I10 I01 (2) 30 parts of l.t-dichlornaphthalene are dissolved, while stirring (in the oil bath) in 63 parts of benzoyl chloride whereupon 60 parts of aluminium chloride are added. The

temperature of the oil bath is gradually raised within 8 hours to 160 C. After cooling, the solidified reaction product is distilled with steam, the product remaining after distillation is twice boiled up with diluted hydrochloric acid, washed until neutral and dried. The product after being purified possesses the same properties as that described in Example 1.

(3) 50 parts of 1.5-dichlornaphthalene are stirred together with 350 parts of carbon disulfide, 38 parts of benzoyl chloride and parts of aluminium chloride for about 15 hours on the water bath under reflex.

By decomposing the mass with water, washing and drying, the solid crude lretone obtained may be distilled in vacuo at about 270 C. to 275 C. under a pressure of 15 mm. in order to purify it. The 8-benzoyl l.5-dichlornaphthalene thus produced recrystallizes from alcohol in colorless, shining prisms, melting at 112 C.

(4) 20 parts of 1.5-dichlornaphthalene are stirred together with 18 parts of pulverized phthalic anhydride and 150 parts of carbon disulfide and 25 parts of aluminium chloride are then introduced. The mixture is kept boiling for 8 hours while stirring. After having decomposed the mass with water and expelled the carbon disulfide, it is boiled up three times with fdiluted hydrochloric acid and twice with water and the residue, after having been made alkaline with caustic soda solution, is distilled with steam in order to free it fromdichlornaphthalene. The undissolved content of the matrass is filtered off and the reaction product dissolved in the filtrate, is precipitated by means of an acid. The colorless body thus obtained dissolves in concentrated sulfuric acid to a yellow solution, turns red-violet.

(5) 1.4 dichlor 8- (para chlorbenzoyl naphthalene: 100 parts of 1.4-dichlornaphthalene, 88 parts of para-chlorbenzoyl chloride and 135 parts of aluminium chloride are introduced into 500 parts of carbon disulfide and the mixture is stirred for 20 hours on the water bath under reflux. The reaction mixture is decomposed with ice water, distilled with water vapor for2 hours, then "crystallized from ethyl alcohol.

which on heating chlornaphthalene. The tough yellow oil thus obtained is triturated with much alcohol and thus obtained in a crystalline form. In-order to purify it further, it may be reprodlgzt forms colorless needles melting at 118 (6) 1.4-dichloro-8- (ortho chlorobenzoyl) naphthalene: 57 parts of 1.4-dichloronaphthalene, 50 parts of ortho-chlorbenzoyl chloride and 80 parts of aluminium chloride are introduced into 300 parts of carbon disulfide and the whole is stirred for 15 hours at about 50 C.

The reaction product is worked up as indicated in the preceding example. It forms colorless prisms when recrystallized from alcohol and melts at 122 C. to 123 C.

(7) 1.4-dichloro-8- (a-naphthoyl) -naphthalene: 50 parts of lA-dichloronaphthalene, 50 parts of a-naphthoyl chloride and 70 parts of aluminium chloride are introduced into 300 parts of carbon disulfide and the whole is kept boiling for 20 hours on the water bath under reflux. The reaction prodnot, when treated in the usual manner may directly be obtained in crystallized form from glacial acetic acid with an addition of animal charcoal. The final product forms yellowish prisms melting at 163 C. to 164 C.

(8) 1.4-dichloro-8- (B-naphthoyl) -naphthalene: parts of 1.4-dichloronaphthalene. 75 parts of ,B-naphthoyl chloride, 105 parts of aluminium chloride are introduced into 450 parts of carbon disulfide and the mixture is stirred for 12 hours on the water bath under reflux. The ketone, after being worked up in the usual manner constitutes when cold a very brittle, brown resin, which can be recrystallized from glacial acetic acid.

(9) 1.4-dichloro-8- (para-toluyl) -naphthalene: 100 parts of 1.4-dichloronaphthalene, parts of para-toluic acid chloride, 135 parts of aluminium chloride are introduced into 500 parts of carbon disulfide and the mixtureis stirred for 15 hours on the water bath under reflux. The product is worked up as above indicated. The crude ketone is purified by distillation in vacuo, the fraction distilling over between 275 C. and 280 C. (under 15 mm. pressure) being collected. The light-yellow resin, which when cold becomes brittle, is obtained by recrystallization from glacial acetic acid in small colorless prisms. Theresulting substance melts after a previously extensive sintering at 135 C. but not sharply. V

(10) 100 parts of lA-dichloronaphthalene, 80 parts of ortho-toluyl chloride, 136 parts of aluminium chloride'are introduced The finalinto 500 parts of carbon disulfide and the mixture is stirred on the water bath for 20 hours under reflux. The product is worked up as indicated in the preceding example. The bright yellow resin obtainable by distillation in vacuo shows only a slight tendency to crystallization. It crystallizes from alcohol in colorless prisms, melting at 91 C. to 92 C. It dissolves in concentrated sulfuric acid to a yellow solution.

(11) 100 parts of 1.4-dichloronaphthalene,

45 parts of acetyl chloride and 135 parts of aluminium chloride are introduced into 500 parts of carbon disulfide and the mixture is stirred for 15 hours under reflux. The reaction product, after being worked up in the usual manner is purified by repeated distillation in vacuo. It boils at 250 C. under a pressure of 13 mm. and forms a yellow oil, having very slight tendency to crystallization.

(12) 57.2 parts of 1.4-dibromnaphthalene and 30 parts of benzoyl chloride are dissolved in 300 parts of carbon disulfide and there are then introduced 55 parts of pulverized aluminium chloride at room temperature. After heating the whole for 4 hours on the water bath, it is decomposed with water and worked up as indicated in the preceding examples.

By recrystallizing from alcohol or glacial acetic acid, colorless needles are obtained.

Instead of carbon disulfide, any other suitable diluent may be used in the examples, such as for instance nitrobenzene.

We claim:

1. As new products, the compounds of the following formula CO Hlg wherein R stands for alkyl or aryl, Hlg for a halogen atom, one of the Xs for a halogen atom, the other X for hydrogen being colorless, well crystallizing compounds, dissolving in concentrated sulfuric acid with a yellow to orange-yellow coloration.

2. As new products, the compounds of the following formula wherein R stands for alkyl or aryl, one of the Xs for chlorine, the other X for hydrogen, being colorless, well crystallizing compounds, dissolving in concentrated surfuric acid with a yellow to orange-yellow coloration.

3. As new products, the compounds of v the following formula i 00 (Ill wherein R represents a phenyl group, which may be substituted byhalogen, methyl or the carboxy group, being colorless, well crystallizing compounds, dissolving in concentrated sulfuric acid with a yellow to orangeyellow coloration.

4. As a new product, the compound of the following formula CsHs or aryl, with a dihalogenated naphthalene in the presence of aluminium chloride.

6. The process which comprises heating an aroylchloride with a dihalogenated naphthtlene in the presence of aluminium chlor1 e.

7 The process which comprises heating a benzoyl chloride in the presence of aluminium chloride and of a diluent with a compound of the group consisting of l/l-dichloronaphthalene and 1.5-dichloro-naphthalene.

8. The process which comprises heating benzoyl-chloride with 1.4-dichloro-naphthalens on a water bath for several hours in the presence of aluminium chloride and carbon disulfide.

9. The process which comprises heating para-chloro-benzoylchloride with 1.l-dichloro-naphthalene on the water bath for several hours in the presence of aluminium chloride and carbon disulfide.

10. The process which comprises heating para-toluic acid chloride with 1.4-dichloronaphthalene on the water bath for several hours in the presence of aluminium chloride and carbon disulfide. 7

11. As a new product, the compound of the following formula:

forming colorless needles melting at 118 C. 12. As a new product, the compound of the following formula:

forming after recrystallization from glacial acetic acid small colorless prisms melting at about 135 C. V In testimony whereof, we aflix our signatures.

GEORG KRANZLEIN. HEINRICH VOLLMANN. ERNST DIEFENBACH. 

